CN109400587A - A kind of red hot activation delayed fluorescence material and the preparation method and application thereof with circular polarised luminescence property - Google Patents
A kind of red hot activation delayed fluorescence material and the preparation method and application thereof with circular polarised luminescence property Download PDFInfo
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Abstract
The object of the present invention is to provide a kind of red hot activation delayed fluorescence material and the preparation method and application thereof with circular polarised luminescence property.Shown in the structural formula of the material such as formula (1) or formula (2), in formula (1) and formula (2), R1、R2It is the Electron rich aromatic amine substituent group containing at least one nitrogen, R1、R2Middle ammonia nitrogen is connected with phenyl ring.Red hot activation delayed fluorescence material provided by the invention with circular polarised luminescence property is formed by organic film with high surface smoothness, heat resistance/water/oxygen, oxidation-reduction resistance, high-luminous-efficiency and hot activation delayed fluorescence property, can be used as the luminescent layer in Organic Light Emitting Diode.
Description
Technical field
The invention belongs to organic electroluminescence device fields, and in particular to a kind of red heat with circular polarised luminescence property
Activate delayed fluorescence material and the preparation method and application thereof.
Background technique
Luminescent material with circular polarised luminescence property is in optical storage of data, optical recognition sensor, quantum calculation, life
Object response imaging, the fields such as optical communication and 3D display for spintronics have potential application.Therefore, CPL
Material and its application have obtained extensive concern, become a new research hotspot in luminous organic material field.Hot activation is prolonged
Slow fluorescent material has small poor (the Δ E of singlet-tripletST) therefore triplet exciton can pass through reversed intersystem crossing
(RISC) it is transformed into singlet excitons to shine, realizes the fluorescent emission that the triplet exciton of non precious metal addition participates in, mention significantly
High luminous efficiency.Such material can make full use of the singlet excitons and triplet exciton for being electrically excited lower formation, make its device
The internal quantum efficiency of part theoretically can achieve 100%, similar to phosphor material, and significantly larger than conventional fluorescent material
25%, become the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material, in recent years by
Extensive concern.
Chiral unit is introduced into TADF skeleton to develop the TADF molecule with CPL, can be extracted from TADF molecule
Effective electroluminescent is without causing damages to polarizer absorption, to save energy in OLED display, is expected to realize tool
There are efficient CP-OLED and stronger CPEL.Although before detailed report the fluorescence chemical combination with CPL feature
Object, but it is less to the compound research with CPL and TADF feature.
Summary of the invention
The object of the present invention is to provide a kind of red hot activation delayed fluorescence material with circular polarised luminescence property.
A kind of red hot activation delayed fluorescence material with circular polarised luminescence property provided by the present invention, structural formula
As shown in formula (1) or formula (2):
In above formula (1) and formula (2), R1、R2It is the Electron rich aromatic amine substituent group containing at least one nitrogen, R1、R2Middle amino
Nitrogen is connected with phenyl ring.
In above-mentioned material, the R1、R2It specifically can be selected from any one in following radicals: 9,9-dimethylacridan-
10- base, phenthazine -10- base, phenoxazine -10- base and spiral shell [acridine -9,9- fluorenes] -10- base, carbazole -9- base, 3,6- di-t-butyl
Carbazole -9- base, 5- phenyl -5,10- dihydrophenazine -10- base, 5- methyl -5,10- dihydrophenazine -10- base, tert-butyl -5 5-,
10- dihydrophenazine -10- base and 9,3 ': 6 ', 9 "-three connection carbazoles -9 '-base.
The present invention also provides the preparation sides of the above-mentioned red hot activation delayed fluorescence material with circular polarised luminescence property
Method includes the following steps:
1) compound shown in formula A and (1S, 2S) -1,2- cyclohexanediamine or (1R, 2R) -1,2- cyclohexanediamine are carried out anti-
It answers, respectively obtains formula B1Or B2Shown compound；
Above formula A, B1And B2In, X is leaving group；
2) by the formula B1Or B2Shown compound is reacted to arrive with the Electron rich aromatic amine containing at least one nitrogen
The red hot activation delayed fluorescence material with circular polarised luminescence property.
In above-mentioned preparation method, compound shown in the formula A and (1S, 2S) -1,2- cyclohexanediamine or (1R,
2R) -1,2- cyclohexanediamine molar ratio can be 2~5:1, concretely 2:1；
The X is selected from least one of fluorine atom, chlorine atom, bromine atom and iodine atom.
In above-mentioned preparation method, in step 1), the reaction carries out in ethanol；
In step 1), the temperature of the reaction can be 78~90 DEG C, and the time of the reaction can be 24~48 hours, specifically
It can be reacted 24 hours under conditions of 78 DEG C.
In above-mentioned preparation method, in step 2), the reaction method of the reaction: in Pd2(dba)3、HPtBu3BF4With
NaOtUnder the conditions of Bu, the Electron rich aromatic amine and the formula B containing at least one nitrogen1Or B2Shown compound is reacted；
The Pd2(dba)3Molar ratio with the Electron rich aromatic amine of at least one nitrogen is 0.1~0.3:1；
The HPtBu3BF4Molar ratio with the Electron rich aromatic amine of at least one nitrogen is 0.3~0.9:1；
The NaOtThe molar ratio of the Electron rich aromatic amine of Bu and at least one nitrogen is 1~3:1；
The formula B1Or B2The molar ratio of the Electron rich aromatic amine of shown compound and at least one nitrogen can for 1:2~
4, concretely 1:2；
The solvent of the reaction is in toluene, tetrahydrofuran, 1,4- dioxane, dimethyl sulfoxide and dimethylformamide
It is at least one；
In step 2), the temperature of the reaction can be 111~125 DEG C, and the time of the reaction can be 24~48 hours, tool
Body can react 24 hours under conditions of 111 DEG C；
In above-mentioned preparation method, the Electron rich aromatic amine containing at least one nitrogen is selected from carbazole, 3,6- di-t-butyl
Carbazole, 9,9-dimethylacridan, phenthazine, phenoxazine and spiral shell [acridine -9,9- fluorenes], 5- phenyl -5,10- dihydrophenazine, 5- first
At least one of base -5,10- dihydrophenazine, 5- tert-butyl -5,10- dihydrophenazine, 9,3 ': 6 ', 9 "-three connection carbazoles；It is preferred that
Ground, the Electron rich aromatic amine containing at least one nitrogen are 9,9- dimethyl acridinium；
Further include in the step 2) to the red hot activation delayed fluorescence material with circular polarised luminescence property into
The step of row purifying；The method of the purifying is using at least one of recrystallization, column chromatography and distillation.
The present invention also provides the red hot activation delayed fluorescence materials with circular polarised luminescence property to be prepared with
Application in machine LED device.
Invention further provides a kind of organic light emitting diode device structure, it includes cathode, anode and organic thin
Film layer；
The organic thin film layer is the luminescent layer containing luminescent material being present between cathode and anode；
The luminescent material that the luminescent layer uses includes the red hot activation of the present invention with circular polarised luminescence property
Delayed fluorescence material.
The specific structure of organic light emitting diode device of the present invention includes any one of following (1)-(4):
(1) anode/hole transmission layer // luminescent layer/electron transfer layer/electron injecting layer/cathode；
(2) anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode
(3) anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer/electron transfer layer/electron injection
Layer/cathode
(4) anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer/hole blocking layer/electron-transport
Layer/electron injecting layer/cathode.
Preferred structure (2) in said structure, but the structure of organic light emitting diode device be not limited to it is recited above
These examples.
Organic light emission is formed by the red hot activation delayed fluorescence material with circular polarised luminescence property of the invention
The preparation method for the luminescent layer that diode uses does not have special limitation.
The present invention is formed a film using vacuum vapour deposition, and the film forming of the vacuum vapour deposition is in general vacuum deposition apparatus
It carries out, the vacuum degree of vacuum chamber can reach 1 × 10 by using diffusion pump and turbomolecular pump-2To 1 × 10-5Pa。
Above method evaporation rate determines that the thickness of formed film, evaporation rate are 0.05~2nm/s.Utilize the present invention
The red hot activation delayed fluorescence material with circular polarised luminescence property is in methylene chloride, chloroform, tetrahydrofuran and toluene
The high property of middle solubility, also can be used conventional device by method of spin coating, ink-jet method, infusion process or casting method come at
Film.
Red hot activation delayed fluorescence material of the present invention with circular polarised luminescence property is formed by organic film
With high surface smoothness, heat resistance/water/oxygen, oxidation-reduction resistance, high-luminous-efficiency and hot activation delayed fluorescence property,
It can be used as the luminescent layer in Organic Light Emitting Diode.
The invention has the following advantages that
(1) present invention tell the red hot activation delayed fluorescence material synthesis method with circular polarised luminescence property it is simple,
Raw material is cheap, products collection efficiency is high, can large scale quantities preparation；(2) and there is hot activation delay property, be not easy racemization, high fluorescence
The characteristics of quantum yield, easy derivatization and the good advantage of stability；(3) prolonged by the red hot activation with circular polarised luminescence property
The organic thin film layer that slow fluorescent material is formed has high efficiency, low driving voltage, length as the Organic Light Emitting Diode of luminescent layer
Service life, circular polarised luminescence the high advantage of dissymmetry factor；It is such to be postponed by the red hot activation with circular polarised luminescence property
The feux rouges Organic Light Emitting Diode that fluorescent material is constructed has a good application prospect.
Detailed description of the invention
Fig. 1 is the reacting flow chart of 1 prepare compound B1 of the embodiment of the present invention.
Fig. 2 is the nucleus magnetic hydrogen spectrum that the embodiment of the present invention 1 prepares gained compound B-11.
Fig. 3 is the nuclear-magnetism carbon spectrum that the embodiment of the present invention 1 prepares gained compound B-11.
Fig. 4 is the reacting flow chart of 3 prepare compound B2 of the embodiment of the present invention.
Fig. 5 is the nucleus magnetic hydrogen spectrum that the embodiment of the present invention 3 prepares gained compound B2.
Fig. 6 is the nuclear-magnetism carbon spectrum that the embodiment of the present invention 3 prepares gained compound B2.
Fig. 7 is the reacting flow chart of 2 prepare compound C1 of the embodiment of the present invention.
Fig. 8 is the nucleus magnetic hydrogen spectrum that the embodiment of the present invention 2 prepares gained compound.
Fig. 9 is the nuclear-magnetism carbon spectrum that the embodiment of the present invention 2 prepares gained compound C1.
Figure 10 is the reacting flow chart of 4 prepare compound C2 of the embodiment of the present invention.
Figure 11 is the nucleus magnetic hydrogen spectrum that the embodiment of the present invention 4 prepares gained compound C2.
Figure 12 is the nuclear-magnetism carbon spectrum that the embodiment of the present invention 4 prepares gained compound C2.
Figure 13 is the structural schematic diagram of the organic electroluminescence device of application examples 1 of the present invention preparation.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto, all of the invention
Any modifications, equivalent replacements, and improvements etc. done within spirit and principle, should all be included in the protection scope of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Raw material as used in the following examples, reagent etc., commercially obtain.
Embodiment 1, preparation B1Shown compound
Reacting flow chart is as shown in Figure 1.
Specific step is as follows:
396g (2mol) A, 115g (1mol) (1S, 2S) -1,2- cyclohexanediamine is sequentially added in 2000mL round-bottomed flask
With 1500mL ethyl alcohol, heats (78 DEG C of the temperature of heating) and flow back 24 hours, be distilled off after reaction system is cooled to room temperature
Then remaining reaction system is placed in progress low temperature recrystallization in 4 DEG C of environment, crude product is obtained by filtration, uses column by 1000mL ethyl alcohol
Thin layer chromatography is purified to obtain the white solid of 326g.The white crystal is compound B1, yield 51.6%.
As depicted in figs. 1 and 2, compound B1Structural identification result it is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.59 (d, J=7.3Hz, 1H), 8.45 (d, J=7.5Hz, 1H),
8.36 (t, J=9.2Hz, 3H), 8.21 (d, J=7.9Hz, 1H), 7.91 (d, J=8.0Hz, 1H), 7.83 (d, J=7.9Hz,
1H), 7.72 (t, J=8.1Hz, 1H), 7.65 (t, J=8.2Hz, 1H), 6.39-6.30 (m, 2H), 2.81-2.61 (m, 2H),
1.97 (dd, J=23.8,10.9Hz, 4H), 1.68 (d, J=11.5Hz, 2H)13C NMR(126MHz,CDCl3)δ163.80,
163.76,132.68,132.57,132.24,131.80,131.46,131.04,130.92,130.76,130.18,129.71,
129.54,128.85,127.94,127.77,123.59,122.77,122.74,121.90,53.30,53.23,29.30,
25.61.
It is confirmed by above-mentioned testing result, compound B1Structure it is correct.
Embodiment 2, preparation C1Shown compound
Reacting flow chart is as shown in Figure 7.
Specific step is as follows:
Under protection of argon gas, the B of 316g (0.5mol) is added into the reactor of the 1000mL equipped with reflux unit1,
9, the 9- dimethyl acridinium of 252g (0.6mol), 4.5g (20mmol) Pd (OAc)2,124.9g(1.3mol)tBuONa,17.4g
(60mmol)HPtBu3BF4And 600mL toluene.(111 DEG C of the temperature of heating) is heated to flow back 24 hours.It is cooled to reaction system
After room temperature, a large amount of water being added to it and methylene chloride is extracted, organic phase extracted is dry with anhydrous sodium sulfate, filters,
Then organic liquid phase is distilled off, obtains crude product.The crude product is purified with column chromatography chromatogram, obtains the red powder of 298g
The red hot activation delayed fluorescence material that end, the as present invention have circular polarised luminescence property.The red powder is C1, yield
It is 66.9%.
As shown in Figure 8 and Figure 9, compound C1Structure detection result it is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.84 (dd, J=7.7,1.0Hz, 1H), 8.70 (dd, J=7.6,
0.8Hz, 1H), 8.65 (dd, J=7.3,1.2Hz, 1H), 8.51 (ddd, J=7.3,3.2,1.2Hz, 1H), 7.98-7.88 (m,
2H), 7.75 (dd, J=7.7,3.6Hz, 1H), 7.68 (d, J=7.8Hz, 1H), 7.62-7.44 (m, 6H), 6.97-6.66 (m,
6H), 6.53 (dq, J=7.9,3.5Hz, 2H), 5.86 (td, J=12.8,8.4Hz, 4H), 2.77 (d, J=23.1Hz, 2H),
2.01 (dd, J=30.9,10.5Hz, 4H), 1.86-1.64 (m, 14H)13C NMR(126MHz,CDCl3)δ164.29,
164.20,163.95,163.90,143.70,143.58,140.01,132.86,132.56,132.23,131.86,130.74,
130.53,130.48,130.26,129.83,129.63,129.52,127.90,127.71,126.65,125.87,124.50,
123.78,123.73,122.97,122.93,121.19,121.12,113.96,113.88,53.54,53.36,53.21,
35.98,32.62,32.59,32.06,29.55,29.39,29.19,25.65.HR-MS(APCI):m/zcalcd for
C60H49N4O4 +[M+H]+889.37408,found 889.37483.
It is confirmed by above-mentioned testing result, obtains chipal compounds C1Structure is correct.
Embodiment 3, preparation B2Shown compound
Reacting flow chart is as shown in Figure 4.
Specific step is as follows:
396g (2mol) A, 115g (1mol) (1R, 2R) -1,2- cyclohexanediamine is sequentially added in 2000mL round-bottomed flask
With 1500mL ethyl alcohol, heats (78 DEG C of the temperature of heating) and flow back 24 hours, be distilled off after reaction system is cooled to room temperature
Then remaining reaction system is placed in progress low temperature recrystallization in 4 DEG C of environment, crude product is obtained by filtration, uses column by 1000mL ethyl alcohol
Thin layer chromatography is purified to obtain the white solid of 344g.The white crystal is compound B2, yield 54.6%.
As shown in Figure 5 and Figure 6, compound B2Structure detection result it is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.59 (d, J=7.4Hz, 1H), 8.45 (d, J=7.3Hz, 1H),
8.36 (t, J=8.3Hz, 3H), 8.21 (d, J=7.8Hz, 1H), 7.90 (d, J=8.0Hz, 1H), 7.82 (d, J=7.9Hz,
1H), 7.72 (t, J=8.0Hz, 1H), 7.64 (t, J=8.0Hz, 1H), 6.33 (d, J=9.2Hz, 2H), 2.69 (d, J=
14.6Hz, 2H), 1.97 (dd, J=24.6,11.0Hz, 4H), 1.69 (t, J=10.4Hz, 2H)13C NMR(126MHz,
CDCl3)δ163.81,163.78,132.72,132.61,132.26,131.82,131.49,131.06,130.94,130.79,
130.22,129.73,129.56,128.89,127.96,127.79,123.61,122.79,122.76,121.92,53.31,
53.25,29.31,25.62.
It is confirmed by above-mentioned testing result, compound B2Structure it is correct.
Embodiment 4, preparation C2Shown compound
Reacting flow chart is as shown in Figure 10.
Specific step is as follows:
Under protection of argon gas, the B of 316g (0.5mol) is added into the reactor of the 1000mL equipped with reflux unit2,
9, the 9- dimethyl acridinium of 252g (0.6mol), 4.5g (20mmol) Pd (OAc)2,124.9g(1.3mol)tBuONa,17.4g
(60mmol)HPtBu3BF4And 600mL toluene.(111 DEG C of the temperature of heating) is heated to flow back 24 hours.It is cooled to reaction system
After room temperature, a large amount of water being added to it and methylene chloride is extracted, organic phase extracted is dry with anhydrous sodium sulfate, filters,
Then organic liquid phase is distilled off, obtains crude product.The crude product is purified with column chromatography chromatogram, obtains the red powder of 290g
The red hot activation delayed fluorescence material that end, the as present invention have circular polarised luminescence property.The red powder is C2, yield
It is 65.2%.
As is illustrated by figs. 11 and 12, compound C2Structure detection result it is as follows:
1H NMR (500MHz, Chloroform-d) δ 8.84 (dd, J=7.7,1.0Hz, 1H), 8.70 (d, J=7.7Hz,
1H), 8.65 (dd, J=7.2,1.1Hz, 1H), 8.51 (ddd, J=7.3,3.3,1.1Hz, 1H), 7.97-7.90 (m, 2H),
7.75 (dd, J=7.7,3.6Hz, 1H), 7.68 (d, J=7.7Hz, 1H), 7.63-7.44 (m, 6H), 6.98-6.66 (m, 8H),
6.58-6.46 (m, 2H), 5.86 (td, J=12.7,8.3Hz, 4H), 2.77 (d, J=23.2Hz, 2H), 2.08-1.92 (m,
4H),1.84–1.63(m,14H).13C NMR(126MHz,CDCl3)δ164.29,164.20,163.95,163.88,
143.68,143.56,140.01,132.87,132.56,132.19,131.82,130.72,130.53,130.48,130.26,
129.84,129.63,129.50,127.90,127.71,126.65,125.87,124.50,123.78,123.73,122.97,
122.94,121.19,121.12,113.96,113.89,53.55,53.39,53.21,35.98,32.71,32.62,32.06,
29.55,29.39,29.19,25.62.HR-MS(APCI):m/z calcd for C60H49N4O4 +[M+H]+889.37408,
found 889.37479.
It is confirmed by above-mentioned testing result, obtains chipal compounds C2Structure is correct.
Application examples 1,
With the red hot activation delayed fluorescence material with circular polarised luminescence property being prepared in the embodiment of the present invention 1
C1For the production and performance evaluation of the organic light emitting diode device of luminescent layer.
(1) with the optical voidness hot activation delayed fluorescence material C based on chiral 1,2- cyclohexanediamine1For the organic of luminescent layer
The making step of electroluminescent device is as follows:
1) it the pretreatment of glass substrate: chooses and has 3 × 3mm2Glass of tin indium oxide (ITO) film figure as transparent electrode
Glass substrate；It is put into ultrasound in ethyl alcohol after being cleaned the glass substrate with pure water, then is handled with plasma cleaner, obtains
To pretreated glass substrate.
2) vacuum evaporation of each layer vacuum evaporation: is carried out with vacuum vapour deposition on the pretreated glass substrate.It is first
First, will treated that glass substrate is put into that vacuum evaporation is intracavitary, be decompressed to 6 × 10-4Pa or less；Then the band shown in Figure 13
There is the glass substrate of ito transparent electrode to start, the organic compound by resistance heating is with the rate of film build of 0.1~0.5nm/s
Carry out vacuum evaporation, successively (1: hole injection layer；2: hole transmission layer；3: luminescent layer；4: electron transfer layer；5: electron injection
Layer；6: cathode) it forms a film.Wherein, the glass substrate with ito transparent electrode is as anode；The HAT-CN of film thickness 10nm
(dipyrazino (2,3-f:2 ', 3 '-h)-quinoxaline-2,3,6,7,10,11-hexacarbonitrile) is as empty
Cave implanted layer；Film thickness is the TAPC (1,1-bis [4- [N, N-di (p-tolyl)-amino] phenyl] of 35nm
Cyclohexane) it is used as hole transmission layer；Film thickness is the CBP (3,3'-di (9H-carbazol-9-yl) biphenyl) of 25nm
With the red hot activation delayed fluorescence material C with circular polarised luminescence property1(doping is than being 95:5) is used as luminescent layer；Film thickness is
The TmPyPB (1,3,5-tri (m-pyrid-3-yl-phenyl) benzene) of 45nm is used as electron transfer layer；Film thickness is 0.9nm
Lithium fluoride as electron injecting layer；Film thickness configures metal mask for the aluminium of 90nm in the mode orthogonal with ITO striped and is constituted yin
Pole obtains Organic Light Emitting Diode.The film thickness is measured with contact pin type elcometer.
3) device encapsulates: the organic electroluminescence device made is sealed in water oxygen concentration 0.1ppm nitrogen atmosphere below
It encloses in glove box, then covers above-mentioned substrate for film deposition using with the vitreous sealing cover of epoxy type ultraviolet curable resin and be used in combination
It is sealed from solidification is dug down, structural schematic diagram is as shown in Figure 9.
(2) with the red hot activation delayed fluorescence material C with circular polarised luminescence property1For the organic light emission of luminescent layer
The performance evaluation of diode:
DC current is applied to made Organic Light Emitting Diode, is commented using Spectrascan PR670 luminance meter
Valence luminescent properties；I-E characteristic is measured using computer-controlled 2400 digital sourcemeter of Keithley.The organic light emission
The luminosity of diode is measured in the case where adding DC voltage change outside.
The CIE chromaticity coordinates value of made organic electroluminescence device is (0.52,0.47), and external quantum efficiency is
11.73%, current efficiency 29.25Cd/A, power efficiency 22.98lm/W.
Application examples 2,
With the red hot activation delayed fluorescence material with circular polarised luminescence property being prepared in the embodiment of the present invention 2
C2For the production and performance evaluation of the Organic Light Emitting Diode of luminescent layer
(1) with the red hot activation delayed fluorescence material C with circular polarised luminescence property2For the organic electroluminescence of luminescent layer
The making step of luminescent device is as follows:
The CBP (3,3'-di (9H-carbazol-9-yl) biphenyl) and tool that film thickness divided by vacuum evaporation is 25nm
There is the red hot activation delayed fluorescence material C of circular polarised luminescence property2Mixture (doping is than being 95:5) is used as outside luminescent layer,
It makes organic electroluminescence device using the same method of application examples 1 of the present invention, and structural schematic diagram is as shown in Figure 9.
(2) with the red hot activation delayed fluorescence material C with circular polarised luminescence property2For the organic light emission of luminescent layer
The performance evaluation of diode:
The CIE chromaticity coordinates value of made organic electroluminescence device is (0.52,0.47), and external quantum efficiency is
11.23%, current efficiency 27.63Cd/A, power efficiency 21.7lm/W.
The present invention has the red hot activation delayed fluorescence material of circular polarised luminescence property in addition to can be used in the application example
Luminescent layer in doping object, apply also for light emitting host layer etc.；Apply also for each of fluorescent material and phosphor material
In kind Organic Light Emitting Diode；In turn, other than the purposes of the imagings such as FPD, apply also for low-power consumption electric power and efficiently
The lighting use etc. of rate.
The above embodiment of the present invention is merely to clearly illustrate examples made by the present invention, and the embodiment party of non-present invention
The restriction of formula.For those of ordinary skill in the art, other not similar shapes can also be made on the basis of the above description
The variation or variation of formula herein can not be exhaustive all embodiments.It is all to belong to technical solution of the present invention institute
The obvious changes or variations amplified out should be at the scope of protection of the present invention.
Claims (10)
1. structural formula such as formula (1) or formula (2) compound represented:
In the formula (1) and formula (2), R1、R2It is the Electron rich aromatic amine substituent group containing at least one nitrogen, R1、R2Middle ammonia nitrogen
It is connected with phenyl ring.
2. compound according to claim 1, it is characterised in that: the R1、R2It is selected from any one in following radicals
Kind: 9,9-dimethylacridan -10- base, phenthazine -10- base, phenoxazine -10- base and spiral shell [acridine -9,9- fluorenes] -10- base, click
Azoles -9- base, 3,6- di-t-butyl carbazole -9- base, 5- phenyl -5,10- dihydrophenazine -10- base, 5- methyl -5,10- dihydro pheno
Piperazine -10- base, 5- tert-butyl -5,10- dihydrophenazine -10- base and 9,3 ': 6 ', 9 "-three connection carbazoles -9 '-base.
3. the preparation method of compound as claimed in claim 1 or 2, includes the following steps:
1) compound shown in formula A and (1S, 2S) -1,2- cyclohexanediamine or (1R, 2R) -1,2- cyclohexanediamine are reacted, point
Formula B is not obtained1Or B2Shown compound；
The formula A, formula B1With formula B2In, X is leaving group；
2) by the formula B1Or B2Shown compound is reacted with the Electron rich aromatic amine containing at least one nitrogen, is obtained right and is wanted
Seek 1 or 2 compounds.
4. preparation method according to claim 3, it is characterised in that: the X be selected from fluorine atom, chlorine atom, bromine atom and
At least one of iodine atom.
5. preparation method according to claim 3 or 4, it is characterised in that: in the step 1), chemical combination shown in the formula A
The molar ratio of object and (1S, the 2S) -1,2- cyclohexanediamine or (1R, 2R) -1,2- cyclohexanediamine is 2~5:1；
In the step 1), the reaction carries out in ethanol；
In the step 1), the temperature of the reaction is 78~90 DEG C, and the time of the reaction is 24~48 hours.
6. the preparation method according to any one of claim 3-5, it is characterised in that: in the step 2), the reaction
In Pd2(dba)3、HPtBu3BF4And NaOtIt is carried out under Bu existence condition；
The Pd2(dba)3Molar ratio with the Electron rich aromatic amine of at least one nitrogen is 0.1~0.3:1；
The HPtBu3BF4Molar ratio with the Electron rich aromatic amine of at least one nitrogen is 0.3~0.9:1；
The NaOtThe molar ratio of the Electron rich aromatic amine of Bu and at least one nitrogen is 1~3:1；
The formula B1Or B2The molar ratio of the Electron rich aromatic amine of shown compound and at least one nitrogen is 1:2~4；
The solvent of the reaction be toluene, tetrahydrofuran, 1,4- dioxane, dimethyl sulfoxide and dimethylformamide at least
It is a kind of；
In the step 2), the temperature of the reaction is 111~125 DEG C, and the time of the reaction is 24~48 hours；
The Electron rich aromatic amine containing at least one nitrogen is selected from carbazole, 3,6- di-t-butyl carbazole, 9,9-dimethylacridan, pheno
Thiazine, phenoxazine and spiral shell [acridine -9,9- fluorenes], 5- phenyl -5,10- dihydrophenazine, 5- methyl -5,10- dihydrophenazine, the tertiary fourth of 5-
At least one of base -5,10- dihydrophenazine, 9,3 ': 6 ', 9 "-three connection carbazoles；Preferably, the richness containing at least one nitrogen
Electronic aromatic amines are 9,9-dimethylacridan.
7. the preparation method according to any one of claim 4-6, it is characterised in that: further include in the step 2) to
To compound purified the step of；The method of the purifying is using at least one of recrystallization, column chromatography and distillation.
8. compound as claimed in claim 1 or 2 is preparing the application in organic light emitting diode device.
9. a kind of organic light emitting diode device structure, it includes cathode, anode and organic thin film layer；
The organic thin film layer is the luminescent layer containing luminescent material being present between cathode and anode；
The luminescent material that the luminescent layer uses includes compound as claimed in claim 1 or 2.
10. organic light emitting diode device structure according to claim 9, it is characterised in that:
The structure of the organic light emitting diode device includes any one of following (1)-(4):
(1) anode/hole transmission layer // luminescent layer/electron transfer layer/electron injecting layer/cathode；
(2) anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode
(3) anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer/electron transfer layer/electron injecting layer/yin
Pole
(4) anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer/hole blocking layer/electron transfer layer/electricity
Sub- implanted layer/cathode.
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| CN113501811A (en) * | 2021-07-16 | 2021-10-15 | 中国科学院化学研究所 | Chiral thermal activation delayed fluorescent material based on aromatic imide and preparation method and application thereof |
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| CN110194734A (en) * | 2019-04-03 | 2019-09-03 | 南京大学 | Chiral fluorescent chemicals and the preparation method and application thereof based on the luxuriant alkane skeleton of ring |
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| CN113501811A (en) * | 2021-07-16 | 2021-10-15 | 中国科学院化学研究所 | Chiral thermal activation delayed fluorescent material based on aromatic imide and preparation method and application thereof |
| CN113461628B (en) * | 2021-07-16 | 2023-02-03 | 中国科学院化学研究所 | Chiral thermal activation delayed fluorescence molecule based on [2.2] para-cyclophane and preparation method and application thereof |
| CN114573507A (en) * | 2022-03-10 | 2022-06-03 | 中国科学院大学 | Thermal activation delayed fluorescent material based on axial chiral ketone receptor and preparation method and application thereof |
| CN114573507B (en) * | 2022-03-10 | 2024-01-23 | 中国科学院大学 | Thermal activation delayed fluorescent material based on axial chiral ketone receptor and preparation method and application thereof |
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